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WO2006084088A1 - Fibre polymere conjuguee, sa preparation et son utilisation - Google Patents

Fibre polymere conjuguee, sa preparation et son utilisation Download PDF

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Publication number
WO2006084088A1
WO2006084088A1 PCT/US2006/003764 US2006003764W WO2006084088A1 WO 2006084088 A1 WO2006084088 A1 WO 2006084088A1 US 2006003764 W US2006003764 W US 2006003764W WO 2006084088 A1 WO2006084088 A1 WO 2006084088A1
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WIPO (PCT)
Prior art keywords
poly
thiophene
thieno
alkyl
haloalkyl
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PCT/US2006/003764
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English (en)
Inventor
Patrick T. Mather
Gregory A. Sotzing
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University of Connecticut
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University of Connecticut
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/26—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from other polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24132—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in different layers or components parallel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]

Definitions

  • Inorganic nanowires and carbon nanotubes are known and have been prepared into nanoelectronics and other devices. These materials are typically prepared by chemical vapor deposition, thereby limiting their ability to be processed.
  • Polymers exhibit a wider range of processability.
  • Polymer nanostructures have been prepared by a variety of methods, including ultra-high energy ultraviolet photolithography, nanoimprint lithography, direct-write lithography, phase separation of block copolymers, electrostatic spinning into nanofibers, and template approaches, to name a few.
  • Conjugated ("conductive") polymers typically contain rigid aromatic backbones, making them difficult to process into nanostructures.
  • conjugated polymer nanostructures are formed by a template approach.
  • a method of preparing a conjugated polymer fiber comprising electrospiniiing a solution of intrinsically conductive polymer, intrinsically conductive polymer precursor, or a combination thereof to form a fiber; and crosslinking the intrinsically conductive polymer, intrinsically conductive polymer precursor, or a combination thereof to form a conjugated polymer fiber.
  • conjugated polymer fibers including nanofibers, prepared by electrospinning; and articles comprising the conjugated polymer fibers or nanofibers.
  • Figure 1 is an exemplary electrostatic spinning apparatus
  • Figure 2a is a field emission scanning electron microscope image (FESEM) of intrinsically conductive polymer precursor nanofibers prepared by electrostatic spinning;
  • Figure 2b is an FESEM image of the nanofibers after solid-state oxidative crosslinking
  • Figure 3 a illustrates a generalized schematic of a system to prepare aligned conjugated polymer fiber
  • Figure 3b is an FESEM image of aligned conjugated polymer fiber
  • Figure 4. is a schematic of a general process of micropatterning conjugated polymer fiber;
  • Figure 5a is an FESEM image of micropatterned lines of conjugated polymer fiber;
  • Figure 5b. is an expanded view of Figure 5a.
  • Conjugated polymer fibers can be prepared using electrostatic spinning of intrinsically conductive polymers (ICP) or intrinsically conductive polymer precursors (ICP precursors) followed by crosslinking of the ICP or ICP precursors to form the conjugated polymer fibers.
  • ICP intrinsically conductive polymers
  • ICP precursors intrinsically conductive polymer precursors
  • Electrostatic spinning is a process similar to a conventional fiber drawing process with the exception that the driving force is an applied electric field.
  • This method takes advantage of the electrostatic repulsions between surface charges.
  • the conjugated polymer fibers produced by this method exhibit different color switching capabilities through modification of the ICP or ICP precursor structure. The color change can switch from one color in the visible spectrum to another. In one example, a blue to orange color switching has been shown for polythiophene conjugated polymer fiber.
  • the conjugated polymer can also exhibit changes in absorption in the infrared and the microwave regions as well. Such polymers can find application in camouflaging heat signals ("thermal camouflage").
  • the conjugated polymer fiber can be prepared from ICP and ICP precursors, which contain a reactive functionality covalently bonded to it that undergoes a reaction in the solid state and/or the swollen state to bring about crosslinking of the ICP or the ICP precursor to generate ICP.
  • the ICP or the ICP precursor may be copolymerized or blended with other non-electrically conducting oligomers and/or polymers that possess reactive functionalities which may also be involved in crosslinking. Suitable ICP and ICP precursors, as well as methods of crosslinking the same are disclosed in U.S. Patent Publication 2004/0242792 A incorporated herein in its entirety.
  • electrostatic spinning can include the use of an apparatus containing three general components: a reservoir (10) with a capillary tip (20), a high voltage power supply (30), and a collector (40) (See Figure 1, not to scale).
  • the reservoir (10) houses a solution of the ICP or ICP precursor that is pumped through a metal capillary (needle) (20) connected to a high voltage DC supply (30) by a metal wire electrode (50).
  • a conductive collector (40), typically metal, is placed at a distance from the capillary tip (20) and is a grounded counter-electrode.
  • a high voltage e.g.
  • the electrode imparts an electrical charge to the pendent drop of solution at the end of the capillary tip.
  • the drop experiences two major types of electrostatic force; the electrostatic repulsion between the surface charges and Coloumbic force exerted by the external electric field.
  • Continuous application of high voltage distorts the suspended liquid drop into a conical shape commonly known as a Taylor cone.
  • the liquid jet (60) ejected from the Taylor cone is continuously elongated with complicated stretching and looping motions while the solvent is evaporated resulting in fibers (70) having diameters of nanometer to micrometer scale.
  • the resulting fibers (70) are deposited on the metallic collector (40) as randomly oriented nonwoven mats or can be collected to form aligned fibers.
  • the choice of ICP or ICP precursor, solvent, and optional components, can be made to provide a solution with the appropriate rheological properties (f ⁇ ]c>l, where [rjj is the intrinsic viscosity of the solution and c is the solution concentration) that electrospin as fibers rather than electrospray as droplets.
  • the solution of ICP or ICP precursor generally comprises the ICP or ICP precursor, optionally non-electrically conducting oligomers or polymers, and a solution solvent.
  • the solution solvent chosen generally results in a dilute solution of the oligomeric and polymeric components rather than a suspension. However, if the solution is too dilute, electrospraying of droplets rather than electrospinning into fibers results.
  • the molecular weight of the polymer can be one factor used to determine the appropriate weight percent of the polymer/polymer precursor used in the electrospinning process. Generally, the higher the molecular weight of the polymer, the more dilute the solution can be that will still allow for fiber formation. Exemplary dilute solutions contain about 1 to about 15 weight percent, specifically about 3 to about 10 weight percent, and more specifically about 6 to about 8 weight percent oligomeric or polymeric components based on the total weight of the solution.
  • the conjugated polymer fiber can be formed into a wide array of diameters, from nanometer to micrometer.
  • the conjugated polymer fiber can comprise a diameter of up to about 1000 nanometers, specifically about 1 nanometer to about 500 nanometers, more specifically about 5 nanometers to about 250 nanometers, yet more specifically about 10 nanometers to about 100 nanometers, and still yet more specifically about 20 nanometers to about 50 nanometers.
  • Nanofibers as used herein means a fiber having an average diameter of less than 1000 nanometers.
  • the solution solvent can be chosen among solvents possessing enough solvating power to allow a solution as concentrated at 15 wt% (for example to yield [ ⁇ ]c>l for typical molecular weights of ICP or ICP precursor), to yield adequate volatility (about 50 0 C ⁇ T bo ii ⁇ about 80 0 C), and to feature an adequately high dielectric constant ( ⁇ r > about 5).
  • Exemplary solution solvents include lower alkyl ethers, such as diethyl ether, tetrahydrofuran, and the like; halogenated alkanes such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and the like; acetonitrile; nitrobenzene; dimethylformamide; N-methylpyrrolidone; or the like, or combinations, including blends, thereof.
  • lower alkyl ethers such as diethyl ether, tetrahydrofuran, and the like
  • halogenated alkanes such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and the like
  • acetonitrile nitrobenzene
  • dimethylformamide dimethylformamide
  • N-methylpyrrolidone or the like, or combinations, including blends, thereof.
  • a potential is applied between the capillary tip of the reservoir and the collector.
  • the potential and distance between the capillary tip and collector is selected so that the effective electrical field strength exceeds about 1 kV/cm, based on experience and depending strongly on surface tension a dielectric constant for the fluid.
  • exemplary potentials of about 8 to about 35 IcV can be applied between the capillary tip and the collector, specifically about 10 to about 25 IcV, and more specifically about 12 to about 15 IcV.
  • the collector can be placed at a distance from the capillary tip of about 2 to about 35 cm, specifically about 5 to about 25 cm, and more specifically about 10 to about 20 centimeters.
  • the electrospun fibers can be formed into random, nonwoven mats, or oriented to form a structure of aligned fibers. Any method known in the art for aligning electrospun fibers can be used. For example, the fibers can be aligned electrostatically (See, e.g., Nanotechnology 12 (2001) pp. 384-390).
  • a nonwoven mat comprising conjugated polymer fiber is prepared by electrospinning a solution of intrinsically conductive polymer, intrinsically conductive polymer precursor, or a combination thereof to form a fiber; collecting the fiber to form a random, nonwoven mat; and crosslinking the intrinsically conductive polymer, intrinsically conductive polymer precursor, or a combination thereof to form a conjugated polymer fiber nonwoven mat.
  • an aligned conjugated polymer fiber structure is prepared by electrospinning a solution of intrinsically conductive polymer, intrinsically conductive polymer precursor, or a combination thereof to form a fiber; collecting the fiber in an aligned configuration to form an aligned fiber structure; and crosslinking the intrinsically conductive polymer, intrinsically conductive polymer precursor, or a combination thereof to form an aligned conjugated polymer fiber structure. Alignment of the conjugated polymer fiber can be used for the polarization of light at different wavelengths while enabling electrochromic switching.
  • the nonwoven mat or the structure of aligned ICP fibers can be "welded" together by optimal exposure to solvent vapor to laterally fuse the fibers together.
  • the solvent plasticizes the polymer allowing the fibers to fuse together and provide mechanical integrity to the mat or structure.
  • a nonwoven fabric of a poly(cyclooctene) (not an ICP precursor, but representative of many thermoplastic fibers) was electrospun from 15 weight percent solution in a mixture of (3:2 v/v) tetrahydrofuran:toluene. As electrospun, the nanofibers were not bonded laterally to each other and the fabric was too weak to handle and easily tore without the support of a substrate film.
  • ICP precursors are non-conductive polymers, oligomers or monomers that can be rendered electrically conductive (i.e. converted into ICPs) by crosslinking the non-conductive polymer, oligomer or monomer.
  • a copolymer of an ICP precursor with a non-electrically conducting polymer or oligomer is also considered to be an ICP precursor.
  • Crosslinking can result in covalent bonding between two intrinsically conductive polymer molecules or between two intrinsically conductive polymer precursor molecules or between an intrinsically conductive polymer molecule and an intrinsically conductive polymer precursor.
  • conjugation within an intrinsically conductive polymer precursor may be simultaneously achieved to convert the intrinsically conductive polymer precursor to an intrinsically conductive polymer.
  • the swollen state as defined herein is that state wherein the ICP or the ICP precursor increases in volume upon exposure to the solvent without completely dissolving in the solvent.
  • the solid state as defined herein is that state wherein the ICP or the ICP precursor is unswollen by solvents.
  • crosslinldng has substantially no affect on the fiber morphology as measured by the average diameter of the fiber before and after crosslinldng.
  • ICPs or ICP precursors include poly(aniline), substituted poly(aniline)s, poly(pyrrole)s, substituted poly(pyrrole)s, poly(thiophene)s, substituted poly(thiophene)s, poly(acetylene)s, poly(ethylenedioxythiophene)s, poly(propylenedioxythiophene)s, poly(ethylenedioxypyrrole)s, poly(propylenedioxypyrrole)s, poly(p-phenylene vinylene)s, polycarbazoles, substituted polycarbazoles, polyindoles, or the like, or combinations comprising at least one of the foregoing ICPs.
  • ICPs or ICP precursors are various combinations of the repeat units of pyrrole, substituted pyrrole, thiophene, substituted thiophene, acetylene, ethylenedioxythiophene, substituted ethylenedioxythiophene, ethylenedioxypyrrole, substituted ethylenedioxypyrrole, vinylene, carbazole, substituted carbazole and the like to give polymer.
  • Blends or copolymers or composites of the foregoing ICPs may also be used.
  • blends or copolymers or composites of an ICP with an ICP precursor may also be used.
  • the ICPs and/or the ICP precursors may be copolymerized with non- electrically conducting oligomers or polymers.
  • non-electrically conducting oligomers and polymers are those that are not intrinsically electrically conductive such as, for example, polyacetals, polyacrylics, polycarbonates polystyrenes, polyesters, polyamides, polyamideimides, polyarylates, polyacrylates, polymethylmethacrylates, polyarylsulfones, polyethersulfones, polyphenylene sulfides, polyvinyl chlorides, polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes, polyetherketones, polyether etherketones, polyether ketone ketones, polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides,
  • the copolymers of the ICPs or ICP precursors with the non-electrically conducting oligomers or polymers may be random copolymers, graft copolymers, block copolymers, star block copolymers, dendrimers, or the like, or combinations comprising at least one of the foregoing copolymers. Blends of ICPs or ICP precursors with other polymers may also be used.
  • the non-electrically conducting oligomers or polymers and the resulting ICPs after oxidative crosslinking of the precursor molecules may generally have molecular weights of about 100 to about 500,000 grams/mole (g/mole). Within this range, it is generally desirable to have molecular weights greater than or equal to about 400, specifically greater than or equal to about 800, and more specifically greater than or equal to about 1000 g/mole. Within this range, it is also desirable to have a molecular weight of less than or equal to about 400,000, specifically less than or equal to about 300,000, and more specifically less than or equal to about 200,000 g/mole.
  • ICPs that may be used include poly(acetylene) and its derivatives shown in (I) below
  • R is alkyl, haloalkyl, alkoxy, or haloalkoxy group and n is greater than 6;
  • R 1 and R 2 may be the same or different and may be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl and wherein n is greater than 6;
  • X is sulfur or oxygen
  • R 1 is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl
  • d is 0 or 1
  • n is greater than 6;
  • X 1 is S 3 O, N-H, N-R 3 where R 3 is alkyl, haloalkyl or, aryl; X 2 and X 3 are the same or different and are C or N; R 1 and R 2 may be the same or different and may be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl and n is greater than 6;
  • R 4 is H, alkyl, haloalkyl or aryl
  • R 1 and R 2 may be the same or different and may be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl, and n is greater than 6;
  • X is sulfur or oxygen
  • R 4 is H, alkyl, haloalkyl or aryl
  • R 1 is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl
  • d is 0 or 1
  • n is greater than 6;
  • R 5 is hydrogen, alkyl, haloalkyl, aryl, or propanesulfonate and R 6 is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, aryl, or sulfonate, and n is greater than 6;
  • R 1 and R 2 are the same of different and are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl, and n is greater than 6;
  • R 1 and R 2 are the same of different and are alkyl, haloalkyl, alkoxy, or haloalkoxy, or aryl, and n is greater than 6;
  • X 1 is S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, and n is greater than 6;
  • X 1 is S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, and n is greater than 6; poly(bithiophene), poly(bifuran), poly(bipyrrole), and derivatives as shown in (XII) below
  • each occurrence of X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, each occurrence of R 1 and R 2 are independently hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or aryl, and n is greater than 6;
  • each occurrence of X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, wherein R 1 and R 2 are the same of different and are alkyl, haloalkyl, alkoxy, or haloalkoxy, or aryl, and n is greater than 6;
  • XV wherein X is S or O, R 1 is alkyl, haloalkyl, alkoxy , haloalkoxy, or aryl, and n is greater than 6;
  • each occurrence of X 1 is independently S, O, N-H 5 N-R 3 where R 3 is alkyl, haloalkyl, or aryl, wherein R 1 and R 2 are the same of different and are alkyl, haloalkyl, alkoxy, or haloalkoxy, or aryl, and n is greater than 6;
  • X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, and n is greater than 6;
  • R 1 and R 2 are the same of different and are alkyl, haloalkyl, alkoxy, or haloalkoxy, or aryl, and n is greater than 6; poly(biindole) and derivatives as shown in (XIX) below
  • each occurrence of R 4 independently is hydrogen, alkyl, haloalkyl, or aryl, and n is greater than 6;
  • each occurrence of X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, each occurrence of R is independently hydrogen or alkyl, and n is greater than 6;
  • X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, and n is greater than 6;
  • X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, and ⁇ represents an aromatic ring system; n is greater than 6;
  • X 1 is independently S, O, N-H, N-R 3 where R 3 is alkyl, haloalkyl, or aryl, and c ⁇ % represents an aromatic ring system; n is greater than 6;
  • n is greater than 6;
  • n is greater than 6;
  • R 4 is independently hydrogen, alkyl, haloalkyl, or aryl, and n is greater than 6;
  • R 4 is independently hydrogen, alkyl, haloalkyl, or aryl, and n is greater than 6.
  • alkyl includes straight chain, branched, and cyclic saturated aliphatic hydrocarbon groups, having the specified number of carbon atoms, generally from 1 to about 12 carbon atoms for the straight chain and generally from 3 to about 12 carbon atoms for the branched and cyclic.
  • alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl, n-pentyl, sec-pentyl, cyclopentyl, and cyclohexyl.
  • Specific alkyl groups include lower alkyl groups, those alkyl groups having from 1 to about 8 carbon atoms, from 1 to about 6 carbon atoms, or from 1 to about 4 carbons atoms.
  • haloalkyl indicates straight chain, branched, and cyclic alkyl groups having the specified number of carbon atoms, substituted with 1 or more halogen atoms, generally up to the maximum allowable number of halogen atoms ("perhalogenated").
  • haloalkyl include, but are not limited to, trifluoromethyl, difluoromethyl, 2- fluoroethyl, and penta-fluoroethyl.
  • alkoxy includes an alkyl group as defined above with the indicated number of carbon atoms attached through an oxygen bridge (-O-).
  • alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, 2- butoxy, t-butoxy, n-pentoxy, 2-pentoxy, 3- pentoxy, isopentoxy, neopentoxy, n-hexoxy, 2- hexoxy, 3-hexoxy, and 3-methylpentoxy.
  • Haloalkoxy indicates a haloalkyl group as defined above attached through an oxygen bridge.
  • aryl indicates aromatic groups containing only carbon in the aromatic ring or rings. Such aromatic groups may be further substituted with carbon or non-carbon atoms or groups. Typical aryl groups contain 1 or 2 separate, fused, or pendant rings and from 6 to about 12 ring atoms, without heteroatoms as ring members. Where indicated aryl groups may be substituted. Such substitution may include fusion to a 5 to 7-membered saturated cyclic group that optionally contains 1 or 2 heteroatoms independently chosen from N, O, and S, to form, for example, a 3,4-methylenedioxy-phenyl group.
  • Aryl groups include, for example, phenyl, biphenyl, terphenyl, naphthyl, including 1- naphthyl and 2-naphthyl, and bi-phenyl.
  • Halo or "halogen” as used herein refers to fluoro, chloro, bromo, or iodo.
  • the ICP is a poly(thiophene).
  • Specific poly(thiophene)s include those having the structural units of the general formulae (XXIX) and/or (XXX):
  • X 4 and Y are either the same or different and may be hydrogen, alkyl, alkoxy, alkoxyalkyl, acyl, alkylene, alkylenedioxy, carboxy, ester, thioacyl, or the like, or combinations of at least one of the foregoing groups having 1 to about 22 carbon atoms, specifically about 1 to about 20 carbon atoms, more specifically about 4 to about 20 carbon atoms, and yet more specifically about 8 to about 18 carbon atoms; and wherein p, m and k may be either the same or different, hi general, p and m independently of one another are integers from about 1 to about 10, specifically integers from about 1 to about 6, and k is an integer from about 1 to about 3000, specifically about 1 to about 1000, and more specifically about 1 to about 100.
  • Exemplary thiophenes that may be used to derive the poly(thiophene) ICPs include 3,4-di(decyl)thiophene, 3,4-di(undecyl)thiophene, 3,4-di(dodecyl)thiophene, 3,4- di(tridecyl)thiophene, 3,4-di(tetradecyl)thiophene, 3,4-di(pentadecyl)thiophene, 3,4- di(hexadecyl)thiophene, 3,4-di(heptadecyl)thiophene, 3,4-di(octadecyl)thiophene, 3,4- di(decyloxy)thiophene, 3,4-di(undecyloxy)thiophene, 3,4-di-(dodecyloxy)thiophene, 3,4- di(tridecy
  • the tliiophene or poly(thiophene) may be copolymerized with a monomer that would form a non-electrically conducting polymer or with more than one monomer that would form a non-electrically conducting polymer.
  • the non-electrically conducting polymer may form the backbone, while the poly(thiophene) or the thiophene is grafted onto the backbone.
  • the thiophene or the poly(thiophene) and the non-electrically conducting polymer may be copolymerized to form alternating copolymers, random copolymers, star block copolymers, block copolymers, multi-block copolymers, hyperbranched copolymers, dendrimers, or the like, or combinations comprising at least one of the foregoing copolymers.
  • the backbone is a norbornylene with the thiophene grafted onto the norbornylene as shown in formulae (XXXI), (XXXII) and (XXXIH):
  • k is about 10 to about 3000, specifically about 20 to about 1000, and more specifically about 50 to about 100.
  • the covalently bonded thiophene graft in the formula (XXXIV) - (XXXVI) may be polymerized by oxidation, either chemically or electrochernically, to form the structure shown in formula (XXXVII) - (XXXIX) below:
  • k is defined above and k 1 is about 1 to about 3000, specifically about 10 to about 1000, and more specifically about 20 to about 100.
  • bis(terthienyl)norbornylene monomer may be polymerized to obtain the poly(thiophene) shown in formula (XL) or formula (XLI):
  • each k 1 is independently about 1 to about 3000, specifically about 10 to about 1000, and more specifically about 20 to about 100.
  • the norbornylene of structures of formula (XL) or formula (XLI) may be later crosslinked if desired to form polynorbornylene.
  • the polymerization of the thiophene to form the poly(thiophene) also promotes crosslinking of the ICP, since a thiophene or poly(thiophene) graft covalently bonded to a first norbornylene backbone generally reacts with a thiophene or poly(thiophene) graft covalently bonded to a second norbornylene backbone, hi the conductive state, there are positive charges on the backbone of the conjugated polymer and negative ions are associated with these positive charges. For example, if ferric chloride were used as the oxidant, then CF would be one of the charge-compensating counter-ions.
  • the ICP precursor is a polynorbornylene according to formulae (XLII) and XLHI):
  • k is about 10 to about 3000, specifically about 20 to about 1000, and more specifically about 50 to about 100;
  • L is a linking group and each Q is independently thiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4- propylenedithiathiophene, 3,4-ethylenedithiathiophene, isathianaphthene, pyridothiophene, pyrizinothiophene, pyrrole, 3,4-ethylenedioxypyrrole, 3,4-ethylenedithiinopyrrole, 3,4- propylenedioxypyrrole, 3,4-propylenedithiinopyrrole, aniline, thionapthene, benzofuran, polyindole, dibenzo thiophene, dibenzofuran, carbazole, bithiophene, bifuran, bipyrrole, thienothiophene, thieno
  • substituents include alkyl, alkoxy, haloalkyl, haloalkoxy, and aryl substituents.
  • the ICP precursor is a polynorbornylene according to formulae (XLIV) and (XLV):
  • substituents for Q include alkyl, alkoxy, haloalkyl, haloalkoxy, and aryl substituents.
  • the linking group L may include, for example ester, amide, carbamate, carbonate, ether, thioether, amine, alkylene, or arylene functionality and chemically stable combinations thereof.
  • the ICP precursor is a polynorbornylene according to formulae (XLVI) and (XLVH):
  • L and L 1 are linl ⁇ ng groups; each Q is independently thiophene, 3,4-ethylenedioxythiophene, 3,4- propylenedioxythiophene, 3 ,4-propylenedithiathiophene, 3 ,4-ethyleneditbiathiophene, isathianaphthene, pyridothiophene, pyrizinothiophene, pyrrole, 3,4-ethylenedioxypyrrole, 3,4- ethylenedithiinopyrrole, 3 ,4-propylenedioxypyrrole, 3 ,4-propylenedithiino ⁇ yr
  • substituents for Q include alkyl, alkoxy, haloalkyl, haloalkoxy, and aryl substituents.
  • the linking groups L and L 1 may include, for example ester, amide, carbamate, carbonate, ether, thioether, amine, alkylene, or arylene functionality and chemically stable combinations thereof.
  • Crosslinldng of the ICP's, ICP precursors, and the non-electrically conducting polymers may be brought about by reacting the aforementioned functionalities via anionic polymerization, cationic polymerization, free radical polymerization, addition polymerization, condensation polymerization, or the like, or combinations comprising at least one of the foregoing methods of polymerization.
  • functional group is thiophene and the crosslinldng is achieved through oxidative radical cation coupling.
  • the crosslinldng can generally be brought about by oxidation. Methods such as chemical oxidation or electrochemical oxidation may be advantageously used to facilitate the crosslinldng.
  • Oxidizing agents such as ammonium peroxydisulphate, potassium persulfate, ferric trichloride (FeCl 3 ), iron (HT) salts such as, but not limited to, iron (DT) tosylate, iron methane sulfonate, salts of permanganates, peracetates, chromates, dichromates, hydrogen peroxide, nitrosyl trifluoromethylsulfonate, nitrosyl bis(trifluoromethylsulfonyl)imide, or the like, or combinations comprising at least one of the foregoing oxidizing agents may be used to facilitate the crosslinldng.
  • electrochemical oxidation electron transfer between the working electrode and the precursor polymer in the presence of electrolyte carries out the
  • Electrolytes for such oxidative polymerization of the precursor polymer include a solvent and a salt.
  • solvents for the electrolyte include water, alcohols such as methanol, ethanol, and the like; acetonitrile, butyrolactone, propylene carbonate, ethylene carbonate, ethylene glycol, diglyme, triglyme, tetraglyme, nitromethane, nitrobenzene, benzonitrile, methylene chloride, chloroform and other solvents having dielectric constants of greater than 2. Salts consist of a cation and an anion.
  • Examples of cations for the salt are sodium, lithium, potassium, magnesium, tetrabutylammonium, tetraethylammonium, other tetraalkyl ammonium by which the alkyl groups on the nitrogen could all be the same or be different and the alkyl groups could be branched or linear, imidazolium, and the like.
  • anions include the halides such as fluoride, chloride, bromide and iodide, perchlorate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(trifluoromethansulfonimide), tosylate, mesylate, dodecylsulfonate and any other sulfonated benzene system, camphor sulfonate, naphthalene sulfonate, and any other aromatic sulfonate including polymeric sulfonates such as polystyrene sulfonate.
  • An exemplary oxidizing agent is ferric trichloride for chemical oxidative crosslmking and the electrolyte is tetrabutylammonium perchlorate for electrochemical oxidative crosslmking.
  • oxidation When oxidation is achieved electrochemically, it is the potential of the working electrode that drives the oxidation.
  • the electrolyte that is used for the electrochemistry will therefore affect the type of ICP that is manufactured. For example, when an ICP is crosslinked in lithium tetrafluoroborate, the tetrafluoroborate will be the charge compensating counter-ion. If lithium perchlorate is used then perchlorate will be the counter-ion.
  • the counter-ion could be hexafluorophosphate, tetrafluoroborate, perchlorate, tosylate, trifluorosulfonamide, trifluoromethanesulfonate, or the like, or combinations comprising at least one of the foregoing counter-ions.
  • the electrolytic medium comprises an electrolyte and a solvent.
  • the electrolyte gives rise to the charge compensating counter-ions.
  • the electrolytic medium may comprise an amount of about 0.1 M to 5 M 5 based on the molarity of the electrolyte, specifically about 0.2 to about 3, and more specifically about 0.3 to about 2 based on the molarity of the electrolyte.
  • the chemical oxidant it is generally desirable to employ a molar ratio wherein the moles of oxidant to the moles of the ICP precursor ranges is in an amount of about 0.5 to about 12, specifically about 0.8 to about 11, more specifically about 1 to about 8, and yet more specifically about 1.5 to about 6.
  • the moles of the ICP precursor is the molecular mass of the polymer repeat unit i.e. the molar mass of the pendant crosslmkable group. For example, if terthiophene is the pendant crosslmkable group, the molar mass of this group would be used for the calculation [0060]
  • dopants are often utilized to convert non-conductive forms of poly(aniline) such as leuco emeraldine to conductive forms of poly(aniline) such as emeraldine or prenigraniline.
  • a dopant as defined here is not the same as that defined within conventional semiconductors like indium-doped tin oxide.
  • the dopant in general, refers to the charge compensating dopant ion.
  • positive charges exist on the polymer backbone and the dopant would be the compensating negative ion, which could be mono, di or trivalent.
  • chloride would be a monovalent ion and sulfate would be a divalent ion.
  • Other "dopant ions" are toluene sulfonate, methanesulfonate, perchlorate, tetrafluoroborate, triflate, or the like, or combinations comprising at least one of the foregoing dopant ions.
  • Doping of the conductive polymer is the process that takes it from the insulating state to the positively charged quinoidal backbone. Doping can be performed electrochemically or chemically. For example, if ferric chloride is used to dope the polymer, then the dopant ion that gets incorporated into the polymer will be chloride.
  • dopants are generally strong acids such as p- toluenesulfonic acid, naphthalene disulfonic acid, methane sulfonic acid, hydrochloric acid, chloromethyl sulfonic acid, fluoromethyl sulfonic acid, oxalic acid, sulfosalicylic acid, trifluoroacetic acid, dodecylbenzene sulfonic acid, or the like, or combinations comprising at least one of the foregoing acids. Dopants are generally added in an amount of about 0.05 moles to about 100 moles per mole of group oxidized.
  • the dopant present in an amount of greater than or equal to about 1 mole per mole of group oxidized, specifically greater than or equal to about 2 moles, and more specifically greater than or equal to about 3 moles, per mole of group oxidized. Within this range it is also desirable to have the dopant present in an amount of less than or equal to about 95 moles, specifically less than or equal to about 90 moles, and more specifically less than or equal to about 75 moles, per mole of group oxidized.
  • Solvents may optionally be used to swell the ICP precursor to the ICP in order to facilitate the crosslinking. As stated above, if a solvent is used, it is desired that the solvent only swell the ICP precursor without completely dissolving it.
  • the solvent utilized for facilitating the crossliriking of the ICP precursor may be one that can swell either the ICP precursor, the non-electxically conducting polymer or oligomer to which the ICP precursor is covalently bonded, or both the ICP precursor and the non-electrically conducting polymer or oligomer to which the ICP precursor is covalently bonded.
  • Liquid aprotic polar solvents such as propylene carbonate, ethylene carbonate, butyrolactone, acetonitrile, benzonitrile, nitromethane, nitrobenzene, sulfolane, dimethylformamide, N-methylpyrrolidone, or the like, or combinations comprising at least one of the foregoing solvents are generally desirable.
  • Polar protic solvents such as, but not limited to, water, methanol, ethanol, propanol, isopropanol, butanol, or the like, or combinations comprising at least one of the foregoing polar protic solvents may be used.
  • non-polar solvents such as a benzene, toluene, methylene chloride, carbon tetrachloride, hexane, diethyl ether, tetrahydrofuran, or the like, or combinations comprising at least one of the foregoing solvents may also be used.
  • Co- solvents comprising at least one aprotic polar solvent and at least one non-polar solvent may also be utilized to modify the swelling power of the solvent and thereby adjust the rate of crosslinking of the ICP or the ICP precursor.
  • Ionic liquids which mainly comprise the imidazolium salts, may also be utilized for swelling the polymer.
  • the crosslinking of the ICP or the ICP precursor fibers in the solid state to form the crosslinked ICP fibers can take place either in the swollen or the unswollen state.
  • the solvent may cause the ICP or the ICP precursor to increase in an amount of about 0.1 volume percent (vol%) to about 300 vol% based on the original volume of the ICP or the ICP precursor.
  • vol% volume percent
  • Crosslinking can take place by chemical oxidation or by electrochemical oxidation.
  • the ICP precursor in the solid or swollen state is generally immersed or dissolved in a solution containing the oxidant.
  • the time period for the immersion may vary depending upon the size of the fiber. In general a time period of about 30 seconds to about 180 minutes is desirable, specifically about 45 seconds to about 160 minutes, more specifically about 1 to about 120 minutes, and yet more specifically about 2 to about 60 minutes.
  • the temperature may be raised or lowered in order to control reaction and diffusion kinetics.
  • temperatures of about -50°C to about 100°C may be employed.
  • Agitation may be optionally utilized during the process of chemical oxidation.
  • the ICP precursors may be optionally swollen with solvent prior to or during the electrochemical oxidation process, if desired.
  • an ICP precursor fiber is generally applied onto a substrate, which can optionally be utilized as the working electrode in an electrochemical cell or the substrate may be an insulator and an external conductive probe or pattern be utilized as the working electrode.
  • Oxidation generally occurs rapidly upon the application of a voltage sufficient to convert the pendant polymerizable unit to a radical cation.
  • the rate of oxidation is dependent upon a number of factors such as, but not limited to, the amount of swelling, the polarity of the solvent, concentration of the precursor monomer units on the backbone of the precursor polymer, the conductivity of the crosslinked ICP formed and the like.
  • a voltage of about 0.1 volt to about 10 volt may be used in the electrochemical cell.
  • the voltage is dependent upon the oxidation potential of the polymerizable unit of the precursor polymer, specifically the voltage is proportional to the voltage that is desirable at the onset for oxidation of the polymerizable unit and more specifically that the voltage be at the peak for polymerizable unit oxidation.
  • the voltage is desirable for the voltage to be less than 1 volt above the peak for polymerizable unit oxidation and more specifically less than 0.8 volt above the peak current for oxidation of the polymerizable unit.
  • a current for galvanostatic electrochemical polymerization of about 0.1 milliamperes/cm 2 to about 20 amperes/cm 2 in the electrochemical cell.
  • a current of greater than or equal to about 0.1, specifically greater than or equal to about 0.3, and more specifically greater than or equal to about 0.5 milliamperes/cm 2 Similarly, within this range, it is desirable to use a current of less than or equal to about 18, specifically less than or equal to about 15, and more specifically less than or equal to about 10 amperes/cm 2 .
  • polythiophene fibers are prepared by electrospinning a solution of ICP comprising thiophene followed by solid-state oxidative crosslinking.
  • FIG. 4 illustrates a generalized scheme of micropatterning conjugated polymer fiber, hi an exemplary embodiment, ICP, ICP precursor, or a combination thereof are formed into a fiber mat (110) onto a substrate surface (100).
  • the ICP or ICP precursor contains reactive groups that can be radiation crosslinked using ultraviolet light, electron beam, vacuum ultraviolet, or gamma radiation.
  • exemplary reactive groups include ethylenic unsaturated groups, for example, arcrylate, methacrylate, arcrylamido, methacrylamido, vinyl, and the like.
  • a photomask (120) is used to provide a desired pattern.
  • FIG. 1 is a Field Emission Scanning Electron Microscope image of micropatterned lines of conjugated polymer fibers. The pale lines are the substrate and the darker lines are the conjugated polymer fiber mat.
  • Figure 5b is a Field Emission Scanning Electron Microscope image of micropatterned lines of conjugated polymer fibers. The pale lines are the substrate and the darker lines are the conjugated polymer fiber mat.
  • Figure 5b is a Field Emission Scanning Electron Microscope image of micropatterned lines of conjugated polymer fibers. The pale lines are the substrate and the darker lines are the conjugated polymer fiber mat.
  • Photoinitiators may optionally be used to promote the photochemical crosslinking. Any suitable photomitiator known in the art can be used, including for example, phosphine oxide photoinitiators, ketone-based photoinitiators, such as hydroxy- and alkoxyalkyl phenyl ketones, and tliioalkylphenyl morpholinoalkyl ketones; and benzoin ether photoinitiators. The exact range of amounts of photoinitiator may be selected by those skilled in the art.
  • Articles prepared from the electrospun fibers are suitable for a wide variety of end use applications where conjugation and/or electrical conductivity is desired, including, for example, antistatic garments, antistatic floor coverings, components in computers, and generally, as replacements for metallic conductors, or semiconductors, including such specific applications, as, for example, batteries, fuel cells, photovoltaics, electrostatic dissipation and electromagnetic shielding. They may also be used for example, as antistatic wrappings for electronic equipment or electromagnetic interference shields for computers and other sensitive instruments, including aerospace applications and biomedical devices.
  • medical applications such as sensors, drag delivery devices, surgical and diagnostic devices and instruments, or components thereof, conductive polymeric wires or leads for activation of biological processes, and antistatic clothing for use by operating room personnel.
  • Still other applications include optoelectronic device components, transistors, capacitors, wires for circuitry, use in interconnect technology, as hole transport layers for light emitting diodes, as light emitting materials for use in light emitting diodes, as optically transparent conductors/electrodes, high surface area electrodes for chemical and tactile sensing and electrical triggering devices, optical gratings and as electrochromic windows or electrochromic displays, including wearable and flexible displays.
  • the fibers can be used as electrochromics in eyewear (goggles, glasses, etc.) for polarizing filters and the like. Still other applications include membranes for food packaging, force transduction, electrically stimulated actuation, light polarization, flexible resistive heating, and optically transparent flexible resistive heating films. [0073] Those structures formed by photolithography find specific application for displays, specifically electrochromic displays as the micropatterning is a way to pixelate a given color; sensors; actuators; optic filters; chemical and particulate filters; and the like.
  • Cast films of ICP precursor 3 were prepared by drop casting 3 onto a platinum button working electrode using tetrahydrofuran (THF) as the casting solvent and the electrochemical solid-state oxidation crosslinking was studied using cyclic voltammetry in a conventional three-electrode cell in tetrabutylammonium perchlorate/acetonitrile (TBAP/CH 3 CN) electrolyte solution.
  • Scheme 2 shows the conversion process of 3 to the crosslinlced conductive polymer 4.
  • the conversion of ICP precursor 3 to conductive polymer 4 occurs in the solid swollen state at a peak potential of ca. 0.78 V.
  • the blue conductive polymer 4 can be converted to orange conjugated polymer 5 via electrochemical reduction. This process of conversion between 4 and 5 is an electrochemically reversible process occurring at a potential of ca. 0.65 V.
  • Example Ib Electrospinning ICP precursor 3 to form ICP precursor fibers:
  • a custom electrospinning apparatus employed a Genie syringe pump (Kent Scientific) operated at a constant volumetric flow rate of 0.04 ml/h.
  • a needle having an inner diameter of 250 micrometers was oriented downward, facing a circular collector (20 cm in diameter) separated 10 cm from the needle tip.
  • the needle tip was positively electrified, nominally 12 IcV 5 through a strain-relieved connection, while the collector was at ground.
  • the tip electrical potential was controlled by a current-limited 30 IcV programmable power supply (Ultravolt, Inc.) that was commanded to ramp linearly to the electrospinning voltage by a Labview program and D/ A converter. The actual voltage was adjusted to ca. 12 IcV in order to balance the electrically-driven flow rate with the delivered volumetric flow rate of the pump.
  • the ICP precursor 3 was prepared into fibers by electrospinning a 7 wt% solution of 3 in THF/DMF (70/30) while applying 1 kV/cm with a tip to collector distance of 10 cm.
  • the fibers produced had a diameter ranging from 120 to 180 nm, with an average diameter size of 140 nm.
  • the diameter of fibers of 3 could be controlled by manipulating the concentration of ICP precursor in the solution. Fibers obtained from 6 wt% solution of 3 in THF/DMF (70/30) while applying 1 kV/cm were found to have a diameter ranging from 90 to 150 nm, with an average diameter size of 110 n. Use of a solution of 3 lower than 4 wt% THF/DMF (70/30) resulted in electrospraying of fine droplets rather than electrospinning.
  • Samples for microscopic observation were taken selectively from sparse regions of the collector, near the edge, with care not to contaminate the fabric composition or the nonwoven morphology.
  • the thin, nonwoven samples were mounted on electron microscopy stubs and coated with a thin layer of Au/Pd (Polaron E5100 SEM Coating Unit) to prevent fiber charging.
  • Electron microscopic imaging was conducted using a Philips ESEM 2020 operated at 20 kV and with images collected on a digital camera.
  • Figure 2a is a field emission scanning electron microscope image of fibers prepared by electrospinning an ICP precursor.
  • Example Ic Formation of conjugated fibers from ICP precursor 3 via chemical solid-state oxidative crosslinking:
  • Intrinsically conductive polymer fibers were prepared by chemical oxidation by dipping the fiber mat of ICP precursor 3 into 0.01 ferric chloride/acetonitrile solution (FeCl 3 /CH 3 CN). In a few minutes, the color of the mat changed from opaque white to deep blue indicating a successful chemical solid-state oxidative crosslinking of fibers. According to SEM images, there were no significant changes in the morphology or diameter of the fibers after the chemical solid-state oxidative crosslinking reaction.
  • Figure 2b is a field emission scanning electron microscope image of crosslinlced fibers after chemical solid-state oxidative crosslinking.
  • Example Id Formation of conjugated fibers from ICP precursor 3 via electrochemical solid- state oxidative crosslinking:
  • Electrochemical solid-state oxidative crosslinking to prepare fibers of 4 was performed in 0.1 M TBAP/CH 3 CN via scanning potentials between 0 V and 1.2 V at a scan rate of 100 mV/s; Ag/Ag + reference (0.455 V vs. SHE). Cyclic voltammetry of this process indicates the success of electrochemical solid-state crosslinking.
  • Fiber mats of 3 due to a refractive index mismatch between air and the polymer, are white in appearance. After solid-state oxidative crosslinking to convert 3 to 4, the fiber mat becomes dark blue in appearance. Upon subsequent reduction of 4 to 5, the fiber mat is orange.
  • Example Ie Formation of a solid-state electrochromic device:
  • FIG. 3 a illustrates a generalized schematic of a system to prepare aligned conjugated polymer fiber from ICP precursor 3 by electrospinning a 3 wt % polymer solution of ICP precursor 3 in THF/DMF 70:30 by weight of the two solvents.
  • the feed rate of the solution was 0.01 ml/hr.
  • Two metallic leads (90), both at ground, are separated across a glass substrate (80).
  • the electrodes were placed 1.6 cm apart with an electrode width of 0.2 cm.
  • Contact is made at both leads and at the capillary tip while applying lkV/cm with a 10cm distance, to give a total of 1OkV. Electrospinning results in the formation of conjugated polymer fibers aligned between the metal leads (90).
  • Figure 3b. is a FESEM image of aligned conjugated polymer fiber.
  • REP ring opening metathesis polymerization
  • the polymer 9 was precipitated 3 times in pentane (300 ml), filtered and then dried under vacuum.
  • the number average molecular weight of the ICP precursor 9 was measured to be 85,350 g/mol as determined by gel permeation chromatography (GPC).
  • the ICP precursor exhibited a polydispersity index of 1.617 and a T g of 55°C.
  • a micropatterning process is generally illustrated in Figure 4.
  • the ICP precursor 9 is spun into a fiber mat (110) onto a glass substrate (100) according to the procedure described in Example Ib above.
  • Negative pattern to the mask, 40 ⁇ m lines of 9 is developed by washing away the un-crosslinked part with chloroform to leave a patterned structure of photocrosslinked polymer mat of photocrosslinked polymer fiber 10 (Scheme 4) on the substrate.
  • FIG. 1 The photocrosslinked polymer mat (130) is then converted to conjugated fibers (140) via electrochemical or chemical solid-state oxidative crosslinking according to the procedures of Example 1, followed by reduction with hydrazine hydrate.
  • Scheme 5 illustrates the conjugated polymer fiber 11.
  • Figure 5a. is a Field Emission Scanning Electron Microscope image of micropatterned lines of conjugated polymer fibers. The pale lines are the substrate and the darker lines are the conjugated polymer fiber mat.
  • Figure 5b. is a close- up of the image of Figure 5 a.; the dark line shown in lower right corner is the edge of the pattern where the ICP precursor polymer mat was removed in the development step.

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Abstract

Fibres polymères conjuguées obtenues au moyen du procédé consistant à électrofiler une solution d'un polymère intrinsèquement conducteur, d'un précurseur de polymère intrinsèquement conducteur ou de leur combinaison afin d'obtenir une fibre et à réticuler le polymère intrinsèquement conducteur, le précurseur de polymère intrinsèquement conducteur ou leur combinaison afin d'obtenir une fibre polymère conjuguée. Cette fibre polymère conjuguée, susceptible d'être une nanofibre, peut être formée en structures de type tapis non tissé ou de type tapis comprenant des fibres polymères conjuguées alignées ou adopter la forme d'un article, notamment d'une fenêtre électrochrome ou d'un dispositif d'affichage. Procédé de préparation d'un micromotif de fibre polymère conjuguée.
PCT/US2006/003764 2005-01-31 2006-01-31 Fibre polymere conjuguee, sa preparation et son utilisation Ceased WO2006084088A1 (fr)

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